CN1934075B - Method for producing (meth)acrylate derivative having isocyanate group - Google Patents
Method for producing (meth)acrylate derivative having isocyanate group Download PDFInfo
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- CN1934075B CN1934075B CN2005800095547A CN200580009554A CN1934075B CN 1934075 B CN1934075 B CN 1934075B CN 2005800095547 A CN2005800095547 A CN 2005800095547A CN 200580009554 A CN200580009554 A CN 200580009554A CN 1934075 B CN1934075 B CN 1934075B
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- isocyanate group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
- C07C263/20—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/16—Preparation of derivatives of isocyanic acid by reactions not involving the formation of isocyanate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/02—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms
- C07C265/06—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
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Abstract
The invention aims to provide a method whereby (meth)acrylate derivatives having an isocyanate group can be obtained in high yield by dehydrochlorination of 3-chloropropionate derivatives having an isocyanate group under industrially advantageous and mild conditions, and the content of residual hydrolyzable chlorine can be reduced. A method for producing a (meth)acrylate derivative having an isocyanate group comprises performing dehydrochlorination of a 3-chloropropionate derivative having an isocyanate group in the presence of a basic nitrogen compound having a tertiary nitrogen, the tertiary nitrogen of the basic nitrogen compound having.
Description
The cross reference of related application
The provisional application of submitting on April 2nd, 2004 according to 35U.S.C the 111st (b) bar 60/558 is submitted and enjoyed according to U.S.C the 119th (e) (1) bar to present patent application according to 35U.S.C the 111st (a) bar, 550 and the applying date rights and interests of the provisional application 60/632,949 submitted on December 6th, 2004.
Technical field
The present invention relates to the method that a kind of preparation is used to produce (methyl) acrylate derivative with isocyanate group of various functional polymer materials.
Background technology
(methyl) acrylate derivative with isocyanate group is the compound that is used to produce various functional polymers.
The common method that preparation has (methyl) acrylate derivative of isocyanate group is to make (methyl) acrylic acid salt and aminoalcohol ester and phosgene reaction.As selection, described derivative can pass through pseudoallyl
Azoles quinoline and phosgene reaction are synthetic.But there is the problem that side reaction occurs in these methods, and these side reactions are the addition reactions on the two keys of (methyl) acryl, and during reaction bring out polymerization owing to the existence of two keys, cause loss.
In addition, United States Patent (USP) 2,821,544 (patent documents 1) have advised having with preparation by the 3-chloropropionic acid ester derivative dehydrochlorination that will have isocyanate group the method for (methyl) acrylate derivative of isocyanate group.
But patent document 1 has only been described and has been utilized quinoline (a kind of weakly alkaline tertiary amine) that 3-chloropropionic acid ethyl isocyanate base ester dehydrochlorination is prepared isocyanic acid acryloyl-oxy ethyl ester.And, because the boiling point difference of isocyanic acid acryloyl-oxy ethyl ester and quinoline is very little, be difficult to separate the product that utilizes patent document 1 to obtain by vacuum distilling.In addition, dehydrochlorination carries out under high temperature (160 ℃), therefore needs to add the isocyanic acid acryloyl polymerizable methacrylate of a large amount of polymerization retarders to suppress to be produced.Just as described above, the method for patent document 1 can not satisfy industrial requirement.
In addition, traditional method has the problem that has many hydrolyzable chlorine in the product.When in various application during as raw material, described (methyl) acrylate derivative with isocyanate group that comprises a large amount of hydrolyzable chlorines will have a negative impact.Therefore, need to reduce the content of the hydrolyzable chlorine in the product.
Summary of the invention
The purpose of this invention is to provide a kind of method that can be under the favourable and gentle condition of industry obtains to have (methyl) acrylate of isocyanate group with high yield, and the content of remaining hydrolyzable chlorine is lowered by the 3-chloropropionic acid ester derivative dehydrochlorination that will have isocyanate group.
For addressing the above problem, the inventor has carried out conscientious research.Found that, in the process of the 3-chloropropionic acid ester dehydrochlorination that will have isocyanate group, use the nitrogen compound of specific alkalescence to address the above problem.The present invention finishes on above-mentioned discovery basis.
In other words, the present invention relates to following content:
A kind of preparation has the method for isocyanate group (methyl) acrylate derivative, this method is included in the basic nitrogen compound existence with tertiary N atom and down the 3-chloropropionic acid ester derivative with isocyanate group by formula (1) expression is carried out the dehydrochlorination processing, with preparation (methyl) acrylate derivative with isocyanate group by formula (2) expression, wherein uncle's nitrogen of basic nitrogen compound has the group that at least one is different from aromatic ring yl:
Cl-CH
2-CHR
1-COO-R
2-NCO (1)
CH
2＝CR
1-COO-R
2-NCO (2)
R wherein
1Be hydrogen atom or methyl, R
2Be the alkylidene group or the following alkyl of 1-10 carbon atom that can branching: wherein the cycloalkylidene of 3-6 carbon atom has the alkylidene group of 0-3 carbon atom in its end.
Have the method for (methyl) acrylate derivative of isocyanate group as above-mentioned [1] described preparation, wherein the boiling point that has of basic nitrogen compound is lower than the boiling point of (methyl) acrylate derivative that is produced.
As above-mentioned [1] or [2] described preparation have the method for (methyl) acrylate derivative of isocyanate group, wherein basic nitrogen compound is a trialkylamine.
Have the method for (methyl) acrylate derivative of isocyanate group as above-mentioned [1] described preparation, wherein basic nitrogen compound is insoluble to reaction solvent.
Have the method for (methyl) acrylate derivative of isocyanate group as above-mentioned [4] described preparation, the basic nitrogen compound that wherein is insoluble to reaction solvent is the ion exchange resin with uncle's nitrogen.
Have the method for (methyl) acrylate derivative of isocyanate group as each described preparation in the item of above-mentioned [1]-[5], wherein said dehydrochlorination carries out under 40-120 ℃.
Have the method for (methyl) acrylate derivative of isocyanate group as each described preparation in the item of above-mentioned [1]-[6], wherein behind described dehydrochlorination, distill to remove remaining basic nitrogen compound.
Have the method for (methyl) acrylate derivative of isocyanate group, wherein radicals R as each described preparation in the item of above-mentioned [1]-[7]
2It is the alkylidene group of 1-10 carbon atom that can branching.
Have the method for (methyl) acrylate derivative of isocyanate group, wherein R as above-mentioned [8] described preparation
2Be-CH
2-CH
2-or-CH
2-CH
2-CH
2-.
Have the method for (methyl) acrylate derivative of isocyanate group as each described preparation in above-mentioned [1]-[9], wherein dehydrochlorination carries out in the presence of the amount of the chlorine 0.5-10 mole that decomposes by every mole of theobromine in the solution of described basic nitrogen compound in the 3-chloropropionic acid ester derivative with isocyanate group that comprising formula (1).
Have the method for (methyl) acrylate derivative of isocyanate group as each described preparation in the item of above-mentioned [1]-[10], wherein the concentration of the hydrolyzable chlorine in the isolating product by simple distillation is no more than 300ppm.
(methyl) acrylate derivative by each described method acquisition in the item of above-mentioned [1]-[11] with isocyanate group.
As above-mentioned [12] described (methyl) acrylate derivative with isocyanate group, wherein the concentration of hydrolyzable chlorine is no more than 300ppm.
A kind of method that reduces the content of hydrolyzable chlorine, this method comprises with the basic nitrogen compound processing with uncle's nitrogen and comprising by (methyl) acrylate derivative with isocyanate group of formula (2) expression and the solution of hydrolyzable chlorine that wherein uncle's nitrogen has the group that at least one is different from aromatic ring yl:
CH
2＝CR
1-COO-R
2-NCO (2)
R wherein
1Be hydrogen atom or methyl, R
2Be the alkylidene group or the following alkyl of 1-10 carbon atom that can branching: wherein the cycloalkylidene of 3-6 carbon atom has the alkylidene group of 0-3 carbon atom in its end.
The invention effect
According to the present invention, (methyl) acrylate derivative with isocyanate group can obtain with high yield by the 3-chloropropionic acid ester derivative dehydrochlorination with isocyanate group under the favourable and gentle condition of industry, and can reduce the content of remaining hydrolyzable chlorine.
And (methyl) acrylate derivative with isocyanate group that obtains by the inventive method comprises polymerisable vinyl double bond and isocyanate group in molecule.Therefore, this derivative can with unsaturated compound as (methyl) acrylate (for example methyl methacrylate and methyl acrylate) or styrene copolymerized so that the material of the functional polymer with isocyanate group to be provided.In addition, introduce unsaturated double-bond, make material can pass through UV-light, electron beam and thermofixation by isocyanate group and the monomer with reactive hydrogen such as hydroxyl, amino or carboxyl, oligopolymer or polymer reaction.
Therefore, the material that comprises derivative of the present invention is applicable to multiple application, comprising resistance, tackiness agent with as the film of electronic material, dental material, medical material, coating and tackiness agent.
Implement best mode of the present invention
Below, describe the present invention's preparation in detail and have the method for (methyl) acrylate of isocyanate group.Just as used herein, term " (methyl) acryl " refers to acryl or methacryloyl, and term " (methyl) acryloyl-oxy " refers to acryloyl-oxy or methacryloxypropyl.
The method that the present invention produces (methyl) acrylate derivative with isocyanate group is in the presence of following specific basic nitrogen compound the 3-chloropropionic acid ester derivative with isocyanate group (hereinafter referred to as " compound (1) ") by formula (1) expression to be carried out the reaction of dehydrochlorination:
Cl-CH
2-CHR
1-COO-R
2-NCO (1)
(methyl) acrylate with isocyanate group that obtains by the inventive method is the compound of being represented by formula (2) (hereinafter referred to as compound (2)):
CH
2＝CR
1-COO-R
2-NCO (2)
In formula (1) and (2), R
1Be hydrogen atom or methyl, R
2Be the alkylidene group or the following alkyl of 1-10 carbon atom that can branching: wherein the cycloalkylidene of 3-6 carbon atom has the alkylidene group of 0-3 carbon atom in its end.
Radicals R
2The alkylidene group of 1-10 carbon atom that preferably can branching is more preferably-CH
2-CH
2-(ethylidene) or-CH
2-CH
2-CH
2-(propylidene), especially preferably-CH
2-CH
2-(ethylidene).
Compound (1) can unrestrictedly use the known method preparation.Usually, it can prepare with dihalo carbonic ether such as phosgene reaction by the 3-chloropropionic acid amino ester derivative that forms between 3-chlorpromazine chloride derivative and amino alcohol hydrochloride (hereinafter referred to as " compound (3) ") of following formula (3) representative:
Cl-CH
2-CHR
1-COO-R
2-NH
2Protonic acid (3)
R wherein
1And R
2Described suc as formula (1) and (2).
Protonic acid shown in the formula (3) does not have particular restriction, and the angle that occurs hydrogenchloride from reaction is afterwards had in mind and is preferably hydrochloric acid.
R wherein
1Be hydrogen and R
2For (the 2-amino-ethyl) of the formula (3) of ethylidene but the 3-chlorpromazine chloride and the 2-monoethanolamine hydrochloride prepared in reaction of 3-chloropropionic acid hydrochloride through type (4) expression:
Cl-CH
2-CH
2-COCl (4)
The compound (3) different with (2-amino-ethyl) 3-chloropropionic acid hydrochloride can be by similar method preparation.Compound (3) can be by obtaining in the salt that hydrogenchloride is added amino (methyl) acrylate.The preferred starting compound that uses unparalleled key to be avoiding polymerization, thereby produces industrial advantage.
Dehydrochlorination carries out in the presence of basic cpd usually.Described basic cpd generally is nitrogenous basic cpd.The residual hydrogen atom on the nitrogen and the isocyanic ester radical reaction of raw material and product cause yield to reduce usually and the alkalescence of nitrogen-atoms disappears.
Therefore, the inventive method adopts the basic nitrogen compound with uncle's nitrogen.
Term " basic nitrogen compound " with uncle's nitrogen for aforesaid on nitrogen-atoms the basic nitrogen compound of no residual hydrogen atom.But wherein the alkalescence of the weakly alkaline nitrogen compound (as quinoline) of nitrogen-atoms formation part aromatic ring is inadequate.Therefore, in order to carry out dehydrochlorination effectively, should not use such compound.Wherein bond all is that the nitrogen compound such as the triphenylamine of aromatic ring yl also is not preferred to all groups of nitrogen-atoms.Term " aromatic ring group " comprises the heterocycle that has with the similar conjugate system of aromatic ring group, and can have substituting group on the ring.
Be used for the inventive method committed step, be that the basic nitrogen compound with uncle's nitrogen of dehydrochlorination need comprise the nitrogen that is different from group (as the alkyl) bond of aromatic ring group with at least one.More preferably, an aromatic ring and described uncle's nitrogen bond at the most.A plurality of groups can bond form ring structure together, but except the structure (as quinoline) that alkalescence reduces.
The example of basic nitrogen compound comprises trialkylamine, wherein form the compound of ring structure (can comprise oxygen, sulphur or other nitrogen-atoms in the ring) with two or three alkyl of nitrogen-atoms bond, wherein be the amine (N for example of aromatic ring group with one of group of nitrogen bond, N-dialkyl aniline and N, N-dialkyl amino yl pyridines).
Concrete example comprises Trimethylamine 99, triethylamine, tripropyl amine, dimethylethyl amine, the dimethyl isopropylamine, diethylmethyl amine, dimethylbutyl amine, the dimethyl hexyl amine, diisopropyl ethyl amine, dimethylcyclohexylam,ne, tetramethyl-diamino methane, dimethyl benzyl amine, Tetramethyl Ethylene Diamine, tetramethyl--1, the 4-diaminobutane, tetramethyl--1, the 3-diaminobutane, tetramethyl--1, the 6-diamino hexane, five methyl diethylentriamine, the 1-methyl piperidine, the 1-ethyl piperidine, N, N-lupetidine (piperadine), N-methylmorpholine, 1,8-diazabicyclo [5.4.0]-7-hendecene (DBU), 1,5-diazabicyclo [4.3.0]-5-nonene (DBN), 2,4-diazabicyclo [2.2.2] octane (DABCO), N, accelerine, N, N-Diethyl Aniline and ion exchange resin with uncle's nitrogen.
Wherein, Trimethylamine 99, triethylamine, tripropyl amine and Tetramethyl Ethylene Diamine are preferred.Basic nitrogen compound can use separately or two or more are used in combination.
In the present invention, described dehydrochlorination can use by the synthetic reaction liquid that forms of compound (1) and implement.Synthetic compound (1) can also be by purifications such as distillations as mentioned above.Preceding kind situation has given industrial advantage, and for example production stage is less.
The basic nitrogen compound that is retained in the dehydrochlorination product of inclusion compound (2) can cause compound (2) polymerization.Therefore, described product is preferably purified to remove nitrogen compound by distillation.
Therefore, for high purity separation, be used for basic nitrogen compound of the present invention and must have than the low boiling point of (methyl) acrylate derivative that is produced.Preferably, the boiling point of described product and basic nitrogen compound differs 20 ℃ or higher, more preferably 30 ℃ or higher.For example, when product was isocyanic acid acryloyl-oxy ethyl ester (boiling point: 200 ℃), basic nitrogen compound preferably had and is lower than 180 ℃ boiling point.Under the situation of isocyanic acid methacryloyl 2-ethoxyethyl acetate (boiling point: 211 ℃), basic nitrogen compound preferably has and is lower than 190 ℃ boiling point.
About wanting isolating basic nitrogen compound, this basic nitrogen compound can be insoluble to employed solvent in the reaction.The example of such basic nitrogen compound comprises the ion exchange resin of being made up of the polymeric basic nitrogen compound.
In theory, described dehydrochlorination can be undertaken by the basic nitrogen compound of use with every mole compound (1) equimolar amount.Basic nitrogen compound can excessively use, but can cause and can cause the remaining basic nitrogen compound of polymeric according to condition.On the other hand, basic nitrogen compound in shortage can cause the residual and reaction of compound (1) not exclusively.When reaction liquid comprises the chlorine that many hydrogenchloride deutero-that occurred by the isocyanate group production period can alkalescence decompose, may produce this situation.
Therefore, be used to reach target compound (2) best result from the basic nitrogen compound optimum quantity of yield with change in reaction conditions.Particularly, when described dehydrochlorination use by compound (1) synthetic forms but when not having the reaction liquid enforcement of separating compound (1) therefrom, will be referred to more factors.Therefore, the basic nitrogen compound optimum quantity determine become more difficult.
In these cases, the amount of basic nitrogen compound is determined ideally according to the measured quantity of the chlorine of theobromine decomposition in the reaction liquid.Particularly, the usage quantity of basic nitrogen compound is to decompose the 0.5-10 mole of chlorine by every mole of theobromine being measured, preferred 0.8-5.0 mole, more preferably 0.9-2.0 mole.The dehydrochlorination reaction of carrying out thus will provide (methyl) with isocyanate group acrylate derivative from yield with high score.Just as used herein, term " chlorine that theobromine decomposes " means the chlorine that can measure under the analysis condition that this paper describes later.
Carry out after the reaction liquid of compound (1) is by purifications such as distillations under the situation of described dehydrochlorination reaction, basic nitrogen compound can be by every mole compound (1) 0.5-10 mole, preferred 0.8-5.0 mole, the more preferably amount use of 0.9-2.0 mole.
In the methods of the invention, dehydrochlorination is in the presence of the above-mentioned basic nitrogen compound and simultaneously temperature is remained under the condition of specified level and carry out.Reaction at high temperature can cause compound (2) polymerization.Therefore, temperature of reaction is desirably 40-120 ℃, preferred 40-100 ℃.
The basicity of reaction times with temperature of reaction and basic nitrogen compound changes, and is generally preferred 30 minutes-30 hours about 10 minutes-40 hours.
Described reaction can be used not the solvent with the isocyanic ester radical reaction.The example of solvent comprises aprotic solvent, for example hydrocarbon such as toluene and dimethylbenzene; Acetic ester such as ethyl acetate, propyl acetate and butylacetate; With chloro solvent such as toluene dichloride.The boiling point of solvent preferably is lower than the boiling point of product.
Behind dehydrochlorination, can remove formed hydrochloride.Filtration is the method for typically removing.Aspect operability of removing hydrochloride and handling property, it is favourable using solvent in reaction.When in being reflected at the low solvent of water solubility, carrying out, the extraction of hydrochloride used water.In order to reduce the decomposition of target product, extraction is preferably carried out after the excesses of basic nitrogen compound is neutralized.
When remaining basic nitrogen compound had separated behind dehydrochlorination and removed hydrochloride as required, compound (2) separated by distillation, crystallization, extraction or column chromatography, preferably passes through fractionation by distillation.
Distillation procedure and the equipment that is used for separating compound (2) there is not particular restriction.The equipment that rectifying and backflow instrument are installed is preferred.Also can use thin-film evaporator.The thermal history to prevent from not expect is preferably carried out in distillation at low temperatures, and generally carries out under 120 ℃ or lower internal temperature.During distilling, can in system, supply with by the oxygen of inert gas dilution or nitrogen protoxide to prevent the product polymerization.
As isolating result, can obtain (methyl) acrylate derivative that hydrolyzable chlorine content wherein is no more than 300ppm with high yield with isocyanate group.
And, as required, can be by handle the content that (methyl) acrylate derivative with isocyanate group reduces hydrolyzable chlorine with above-mentioned basic nitrogen compound.In the case, basic nitrogen compound can be by the 0.1-10 mole of every mole of hydrolyzable chlorine, preferred 0.2-5.0 mole, the more preferably amount use of 0.3-2.0 mole.
Above-mentioned processing exists and simultaneous temperature remains under the condition of specified level and carries out at above-mentioned basic nitrogen compound.Processing under the high temperature can cause the polymerization of (methyl) acrylate derivative.Therefore, treatment temp is desirably 10-120 ℃, is preferably 10-100 ℃, more preferably 10-80 ℃.
Embodiment
Below, by embodiment the present invention is described in more detail.But the present invention is not subjected to the restriction of these embodiment.
In an embodiment, the chlorine and the hydrolyzable chlorine of following measurement theobromine decomposition:
(chlorine that theobromine decomposes)
The 300ml erlenmeyer flask that has stopper is put in the accurate weighing of about 0.5 g sample, and the 100ml methyl alcohol of in this flask, packing into/purified water mixture (volume ratio: 70/30).Further, the aqueous sodium hydroxide solution that adds 10ml30%.Afterwards, prolong is installed on this erlenmeyer flask and under refluxing in 80 ℃ of heating in water bath 1 hour, then cool to room temperature.Then the solution that is obtained is transferred in the 200ml measuring bottle, and in this bottle, packed into purified water up to scale marks.Accurately measure 10ml liquid and put into the 200ml beaker, then add 100ml purified water and 1ml (1+1) nitric acid.Then, use 1/50 standard silver nitrate solution that the liquid that is obtained is carried out the concentration of potentiometric titration with the chlorine of mensuration theobromine decomposition.Potentiometric titration uses automatic titrator (COM-550, by HIRANUMA SANGYO Co., Ltd makes) to carry out.
(hydrolyzable chlorine)
Weighing 5g sample is also put into the 100ml erlenmeyer flask, and pack in this flask 35ml methyl alcohol and 15ml water.Afterwards, reflux exchanger is installed on this erlenmeyer flask and under refluxing in 80 ℃ of heating in water bath 30 minutes, then cool to room temperature.Then, use 1/100 standard silver nitrate solution that the liquid that is obtained is carried out potentiometric titration to measure the concentration of hydrolyzable chlorine.
＜synthesis example 1 〉
Synthetic 3-chlorpromazine chloride
Pack in a four-hole boiling flask that is equipped with thermometer, cooling tube, gas inlet pipe and agitator 50g vinylformic acid and 1g dimethyl formamide then are heated to 70 ℃.Afterwards, in 10 hours time, supply with the 100g phosgene.After supply with finishing, remove excess phosgene and carry out vacuum distilling (under 60 ℃ and 3kPa).Separate the first cut 5g, the 3-chlorpromazine chloride obtains as the amount (yield 80%) of main fraction with 50g.
＜synthesis example 2 〉
Synthetic 3-chloropropionic acid (2-ethyl isocyanate base) ester
Pack in a four-hole boiling flask that is equipped with thermometer, cooling tube, gas inlet pipe and agitator 250ml toluene and 25g (0.41mol) 2-monoethanolamine then are heated to 90 ℃.Then, supply with about 20g hydrogenchloride.Then, the 3-chlorpromazine chloride that Dropwise 5 9g (0.46mol) obtains in synthesis example 1 in 90 minutes time, and under 90 ℃, heated 1 hour.Further, in 4 hours time, supply with 80g (0.81 mole) phosgene.Afterwards, remove dissolved phosgene and toluene and distill (under 105-110 ℃ and 0.7kPa).Like this, 3-chloropropionic acid (2-ethyl isocyanate base) ester obtains with the amount (0.33 mole) (yield 81%) of 59g.
＜synthesis example 3 〉
Synthetic 3-chloro-2 Methylpropionic acid (2-ethyl isocyanate base) ester
3-chloro-2-methyl-prop acyl chlorides utilizes the step of synthesis example 1 synthetic, but vinylformic acid is replaced with methacrylic acid.Subsequently, utilize the step of synthesis example 2 to prepare 3-chloro-2 Methylpropionic acid (2-ethyl isocyanate base) ester, but be to use 3-chloro-2-methyl-prop acyl chlorides.
＜synthesis example 4 〉
Synthetic 3-chloropropionic acid (2-ethyl isocyanate base) ester crude product
Pack in a four-hole boiling flask that is equipped with thermometer, cooling tube, gas inlet pipe and agitator 1200ml toluene and 131g (2.15mol) 2-monoethanolamine then are heated to 90 ℃.Subsequently, supply with about 93g hydrogenchloride.Afterwards, in 90 minutes time, drip the 3-chlorpromazine chloride that 300g (2.37mol) obtains in synthesis example 1, and under 90 ℃, heated 1 hour.Further, in 4 hours time, supply with 373g (3.77mol) phosgene.Afterwards, remove the dissolved phosgene.Like this, the form with 1100g liquid obtains 3-chloropropionic acid (2-ethyl isocyanate base) ester crude product.
The gas chromatographic analysis of liquid finds that the concentration of 3-chloropropionic acid (2-ethyl isocyanate base) ester is 28.6%.In other words, aforesaid method provides 314.6g (1.77mol) 3-chloropropionic acid (2-ethyl isocyanate base) ester (yield 82%).The content that records the theobromine decomposition chlorine in 3-chloropropionic acid (2-ethyl isocyanate base) the ester crude product liquid is 8.33%.
＜embodiment 1 〉
3-chloropropionic acid (2-ethyl isocyanate base) ester and 50g (0.49mol) triethylamine (boiling point: 89.4 ℃) that 250ml toluene, 59g obtain in synthesis example 2 of packing in there-necked flask is then under agitation in 50 ℃ of heating 6 hours.Behind cool to room temperature, the formed hydrochloride of filtering.Subsequently, excessive triethylamine and the toluene of evaporation.With residuum distillation (under 62-67 ℃ and 0.7kPa), obtain 41g (0.29mol) isocyanic acid acryloyl-oxy ethyl ester (boiling point: 200 ℃) (yield 87%).The concentration of hydrolyzable chlorine is 170ppm.
＜embodiment 2 〉
3-chloropropionic acid (2-ethyl isocyanate base) ester and 70g (0.49mol) tripropyl amine (boiling point: 156.5 ℃) that 250ml toluene, 60g (0.34mol) obtains in synthesis example 2 of packing in there-necked flask is then under agitation in 50 ℃ of heating 6 hours.Behind cool to room temperature, the formed hydrochloride of filtering.Subsequently, excessive tripropyl amine and the toluene of evaporation.With residuum distillation (under 62-67 ℃ and 0.7kPa), obtain 39g (0.28mol) isocyanic acid acryloyl-oxy ethyl ester (boiling point: 200 ℃) (yield 82%).The concentration of hydrolyzable chlorine is 200ppm.
＜embodiment 3 〉
250ml toluene, 60g (0.34mol) in there-necked flask, pack at 3-chloropropionic acid (2-ethyl isocyanate base) ester and 28.5g (0.49mol) Tetramethyl Ethylene Diamine (boiling point: 158-160 ℃) that synthesis example 2 obtains, then under agitation heated 6 hours in 50 ℃.Behind cool to room temperature, the formed hydrochloride of filtering.Subsequently, excessive Tetramethyl Ethylene Diamine and the toluene of evaporation.With residuum distillation (under 62-67 ℃ and 0.7kPa), obtain 41g (0.29mol) isocyanic acid acryloyl-oxy ethyl ester (boiling point: 200 ℃) (yield 86%).The concentration of hydrolyzable chlorine is 230ppm.
＜embodiment 4 〉
3-chloropropionic acid (2-ethyl isocyanate base) ester and the 200g exsiccant strong basic ion exchange resin that 250ml toluene, 60g (0.34mol) obtains in synthesis example 2 of packing in there-necked flask is then under agitation in 50 ℃ of heating 6 hours.Behind cool to room temperature, the described ion exchange resin of filtering.Subsequently, evaporation toluene also distills residuum (under 62-67 ℃ and 0.7kPa), obtains 41g (0.29mol) isocyanic acid acryloyl-oxy ethyl ester (boiling point: 200 ℃) (yield 86%).The concentration of hydrolyzable chlorine is 270ppm.
＜embodiment 5 〉
Pack in there-necked flask 3-chloro-2 Methylpropionic acid (the 2-ethyl isocyanate base) ester and 50g (0.49mol) triethylamine (boiling point: 89.4 ℃) that are obtained by synthesis example 3 of 250ml toluene, 66g (0.34mol) are then under agitation in 75 ℃ of heating 30 hours.Behind cool to room temperature, the formed hydrochloride of filtering.Subsequently, excessive triethylamine and the toluene of evaporation.Distillation residuum (under 75-78 ℃ and 0.7kPa) obtains 37g (0.24mol) isocyanic acid methacryloyl 2-ethoxyethyl acetate (boiling point: 211 ℃) (yield 70%).The concentration of hydrolyzable chlorine is 220ppm.
＜embodiment 6 〉
Pack in there-necked flask 3-chloropropionic acid (the 3-propyl isocyanate base) ester and 50g (0.49mol) triethylamine (boiling point: 89.4 ℃) that are obtained by synthesis example 2 of 250ml toluene, 66g (0.34mol) are then under agitation in 50 ℃ of heating 6 hours.Behind cool to room temperature, the formed hydrochloride of filtering.Subsequently, excessive triethylamine and the toluene of evaporation.Distillation residuum (under 72-75 ℃ and 0.7kPa) obtains 35g (0.23mol) isocyanic acid acryloyl-oxy propyl ester (boiling point: 230 ℃) (yield 66%).The concentration of hydrolyzable chlorine is 250ppm.
＜Comparative Examples 1 〉
Pack in there-necked flask 3-chloropropionic acid (the 2-ethyl isocyanate base) ester and 63g (0.49mol) quinoline (boiling point: 237.7 ℃) that are obtained by synthesis example 2 of 250ml toluene, 60g (0.34mol) are then under agitation in 50 ℃ of heating 6 hours.Confirm no isocyanic acid acryloyl-oxy ethyl ester by gas chromatographic analysis.
＜Comparative Examples 2 〉
Pack in there-necked flask 3-chloropropionic acid (the 2-ethyl isocyanate base) ester and 38.8g (0.49mol) pyridine (boiling point: 115-116 ℃) that are obtained by synthesis example 2 of 250ml toluene, 60g (0.34mol) are then under agitation in 50 ℃ of heating 6 hours.Confirm no isocyanic acid acryloyl-oxy ethyl ester by gas chromatographic analysis.
＜Comparative Examples 3 〉
Under the condition that United States Patent (USP) 2821544 embodiment 1 describe, implement following step.Pack in there-necked flask 3-chloropropionic acid (the 2-ethyl isocyanate base) ester and 63g (0.49mol) quinoline (boiling point: 237.7 ℃) that are obtained by synthesis example 2 of 60g (0.34mol) are then under agitation in 160 ℃ of heating 1 hour.Gas chromatographic analysis confirmation 3-chloropropionic acid (2-ethyl isocyanate base) ester has disappeared and has formed isocyanic acid acryloyl-oxy ethyl ester.Reaction liquid is viscosity, dark brown and basic liquid uniformly.This liquid of vacuum distilling forms the 10g cut, remaining viscous liquid.This cut is carried out gas chromatographic analysis, find that the cut that is obtained is the mixture (with about 5: 4 ratio) of isocyanic acid acryloyl-oxy ethyl ester and quinoline.Thereby, do not obtain highly purified isocyanic acid acryloyl-oxy ethyl ester.
＜Comparative Examples 4 〉
Pack in there-necked flask 3-chloro-2 Methylpropionic acid (the 2-ethyl isocyanate base) ester and 63g (0.49mol) quinoline (boiling point: 237.7 ℃) that are obtained by synthesis example 3 of 66g (0.34mol) are then under agitation in 160 ℃ of heating 1 hour.Gas chromatographic analysis confirms that 3-chloropropionic acid (2-ethyl isocyanate base) ester has been reduced and has formed isocyanic acid methacryloyl 2-ethoxyethyl acetate.Reaction liquid is viscosity, dark brown and basic liquid uniformly.This liquid of vacuum distilling forms the 18g cut, remaining viscous liquid.This cut is carried out gas chromatographic analysis, find that the cut that is obtained is the mixture (with about 5: 6 ratio) of isocyanic acid methacryloyl 2-ethoxyethyl acetate and quinoline.Thereby, do not obtain highly purified isocyanic acid methacryloyl 2-ethoxyethyl acetate.
＜embodiment 7 〉
Pack in the 500ml flask liquid of thick 3-chloropropionic acid (the 2-ethyl isocyanate base) ester that is obtained by synthesis example 4 of 111.5g then adds 0.20g phenothiazine and 0.20g 2,6-two-tertiary butyl hydroxytoluene.The liquid of thick 3-chloropropionic acid (2-ethyl isocyanate base) ester comprises 3-chloropropionic acid (the 2-ethyl isocyanate base) ester that can alkalescence decomposes chlorine and 31.9g (0.18mol) of 9.29g (0.26mol).In 1.5 hours time, drip 26.5g (0.26mol) triethylamine then.Subsequently, under agitation in 60 ℃ of heating 8 hours, then cool to room temperature.Formed solid by filtration separation is also used toluene wash.
The gas chromatographic analysis of gained liquid confirms to have obtained 23.4g (0.166mol, yield 92.2%) isocyanic acid acryloyl-oxy ethyl ester.The content of remaining 3-chloropropionic acid (2-ethyl isocyanate base) ester is 2.1%.
＜embodiment 8 〉
Pack in the 500ml flask liquid of thick 3-chloropropionic acid (the 2-ethyl isocyanate base) ester that is obtained by synthesis example 4 of 111.5g then adds 0.20g phenothiazine and 0.20 g 2,6-two-tertiary butyl hydroxytoluene.In 1.5 hours time, drip 25.4g (0.25mol) triethylamine then.Subsequently, under agitation in 60 ℃ of heating 8 hours, then cool to room temperature.Formed solid by filtration separation is also used toluene wash.
The gas chromatographic analysis of gained liquid confirms to have obtained 23.6g (0.167mol, yield 93.0%) isocyanic acid acryloyl-oxy ethyl ester.The content of remaining 3-chloropropionic acid (2-ethyl isocyanate base) ester is 5.0%.
＜embodiment 9 〉
Pack in the 500ml flask liquid of thick 3-chloropropionic acid (the 2-ethyl isocyanate base) ester that is obtained by synthesis example 4 of 111.5g then adds 0.20g phenothiazine and 0.20g 2,6-two-tertiary butyl hydroxytoluene.In 1.5 hours time, drip 39.8g (0.39mol) triethylamine then.Subsequently, under agitation in 60 ℃ of heating 8 hours, then cool to room temperature.Formed solid by filtration separation is also used toluene wash.
The gas chromatographic analysis of gained liquid confirms to have obtained 22.3g (0.158mol, yield 87.7%) isocyanic acid acryloyl-oxy ethyl ester.The content of remaining 3-chloropropionic acid (2-ethyl isocyanate base) ester is 0.3%.
＜embodiment 10 〉
Pack in the 500ml flask liquid of thick 3-chloropropionic acid (the 2-ethyl isocyanate base) ester that is obtained by synthesis example 4 of 111.5g then adds 0.20g phenothiazine and 0.20g 2,6-two-tertiary butyl hydroxytoluene.In 1.5 hours time, drip 63.6g (0.62mol) triethylamine then.Subsequently, under agitation in 60 ℃ of heating 8 hours, then cool to room temperature.Formed solid by filtration separation is also used toluene wash.
The gas chromatographic analysis of gained liquid confirms to have obtained 20.8g (0.147mol, yield 81.7%) isocyanic acid acryloyl-oxy ethyl ester.The content of remaining 3-chloropropionic acid (2-ethyl isocyanate base) ester is 0.1%.
Table 1 has provided yield and the residual substance of embodiment 7-10, the ratio of the chlorine that described data are decomposed with respect to theobromine based on the amount of basic nitrogen compound (triethylamine).
Table 1
| Embodiment | Ratio * | Yield (%) | Residual substance (%) |
| ?7 | ?1.0 | ?92.2 | ?2.1 |
| ?8 | ?0.97 | ?93.0 | ?5.0 |
| ?9 | ?1.5 | ?87.7 | ?0.3 |
| ?10 | ?2.4 | ?82.2 | ?0.1 |
*The chlorine (mole) that triethylamine (mole)/theobromine decomposes
＜embodiment 11 〉
Packing in there-necked flask, (solution that comprises isocyanic acid methacryloyl 2-ethoxyethyl acetate 0.19mol) and 19.1g (0.19mol) triethylamine are then under agitation in 40 ℃ of heating 10 hours for the concentration of hydrolyzable chlorine: 33000ppm, 6.6g for 200g.Behind cool to room temperature, the hydrochloride that filtering forms.Subsequently, the solution that distillation is obtained (under 75-78 ℃ and 0.7kPa) obtains isocyanic acid methacryloyl 2-ethoxyethyl acetate.The concentration of hydrolyzable chlorine is 1092ppm.
＜Comparative Examples 5 〉
(solution that comprises isocyanic acid methacryloyl 2-ethoxyethyl acetate 0.19mol) (under 75-78 ℃ and 0.7kPa) obtains isocyanic acid methacryloyl 2-ethoxyethyl acetate to distillation 200g, and handles without basic nitrogen compound for the concentration of hydrolyzable chlorine: 33000ppm, 6.6g.The concentration of hydrolyzable chlorine is 5262ppm.
Claims (8)
1. method for preparing (methyl) acrylate derivative with isocyanate group, this method is included in the basic nitrogen compound existence with tertiary N atom and down the 3-chloropropionic acid ester derivative with isocyanate group by formula (1) expression is carried out the dehydrochlorination processing, with preparation (methyl) acrylate derivative with isocyanate group by formula (2) expression, wherein uncle's nitrogen of basic nitrogen compound has the group that at least one is different from aromatic ring yl:
Cl-CH
2-CHR
1-COO-R
2-NCO (1)
CH
2＝CR
1-COO-R
2-NCO (2)
R wherein
1Be hydrogen atom or methyl, R
2Be the alkylidene group or the following alkyl of 1-10 carbon atom that can branching: wherein the cycloalkylidene of 3-6 carbon atom has the alkylidene group of 0-3 carbon atom in its end,
Wherein basic nitrogen compound is a trialkylamine.
2. preparation as claimed in claim 1 has the method for (methyl) acrylate derivative of isocyanate group, and wherein the boiling point of basic nitrogen compound is lower than the boiling point of (methyl) acrylate derivative that is produced.
3. preparation as claimed in claim 1 has the method for (methyl) acrylate derivative of isocyanate group, and wherein said dehydrochlorination carries out under 40-120 ℃.
4. preparation as claimed in claim 1 has the method for (methyl) acrylate derivative of isocyanate group, wherein distills behind described dehydrochlorination to remove remaining basic nitrogen compound.
5. preparation as claimed in claim 1 has the method for (methyl) acrylate derivative of isocyanate group, wherein radicals R
2It is the alkylidene group of 1-10 carbon atom that can branching.
6. preparation as claimed in claim 5 has the method for (methyl) acrylate derivative of isocyanate group, wherein R
2Be-CH
2-CH
2-or-CH
2-CH
2-CH
2-.
7. preparation as claimed in claim 1 has the method for (methyl) acrylate derivative of isocyanate group, and wherein said dehydrochlorination carries out in the presence of the amount of the chlorine 0.5-10 mole that described basic nitrogen compound decomposes by every mole of theobromine in the solution of the 3-propanoate ester derivatives with isocyanate group that comprising formula (1).
8. preparation as claimed in claim 1 has the method for (methyl) acrylate derivative of isocyanate group, and wherein the concentration of the hydrolyzable chlorine in the isolating product by simple distillation is no more than 300ppm.
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| JP089363/2004 | 2004-03-25 | ||
| JP2004089363 | 2004-03-25 | ||
| JP2004339776 | 2004-11-25 | ||
| JP339776/2004 | 2004-11-25 | ||
| JP023176/2005 | 2005-01-31 | ||
| JP2005023176 | 2005-01-31 | ||
| PCT/JP2005/005655 WO2005092842A1 (en) | 2004-03-25 | 2005-03-22 | Method for producing (meth)acrylate derivative having isocyanate group |
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| US (1) | US7632965B2 (en) |
| EP (1) | EP1745013B1 (en) |
| JP (1) | JP4823546B2 (en) |
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| US8044235B2 (en) * | 2005-03-15 | 2011-10-25 | Showa Denko K.K. | (Meth) acryloyl group-containing aromatic isocyanate compound and production process thereof |
| CN102119146A (en) * | 2008-08-08 | 2011-07-06 | 昭和电工株式会社 | Method for inhibiting polymerization of ethylenically unsaturated carboxylic acid ester compound containing isocyanate group and method for producing ethylenically unsaturated carboxylic acid ester compound containing isocyanate group |
| EP2377847A1 (en) | 2010-04-14 | 2011-10-19 | 3M Innovative Properties Company | Process for producing isocyanates |
| KR101539160B1 (en) * | 2011-02-15 | 2015-07-23 | 쇼와 덴코 가부시키가이샤 | Stabilized isocyanate group-containing ethylene-based unsaturated compound |
| WO2012111446A1 (en) * | 2011-02-15 | 2012-08-23 | 昭和電工株式会社 | Stabilized isocyanate group-containing ethylene-based unsaturated compound |
| US9221928B2 (en) | 2011-06-20 | 2015-12-29 | Central Glass Company, Limited | Fluorine-containing sulfonate resin, fluorine-containing N-sulfonyloxyimide resin, resist composition and pattern formation method |
| CN103842066B (en) | 2011-09-30 | 2016-08-24 | 日本化成株式会社 | Polymerism inorganic particle dispersion agent, Inorganic whisker particle containing this polymerism inorganic particle dispersion agent and inorganic organic resin composite |
| CN102702028B (en) * | 2012-06-12 | 2013-11-06 | 江苏快达农化股份有限公司 | Method for synthesizing methacryloxyethyl isocyanate |
| CN103193675A (en) * | 2013-03-26 | 2013-07-10 | 浙江同丰医药化工有限公司 | Method for preparing ethyl methacrylate isocyanate |
| JP6195409B2 (en) * | 2013-11-01 | 2017-09-13 | 昭和電工株式会社 | Method for producing unsaturated urethane compound, unsaturated thiourethane compound, unsaturated urea compound or unsaturated amide compound |
| JP6529156B2 (en) * | 2015-02-18 | 2019-06-12 | 昭和電工株式会社 | Composition, method of producing composition and method of producing unsaturated compound |
| US11174337B2 (en) | 2016-10-14 | 2021-11-16 | Asahi Kasei Kabushiki Kaisha | Isocyanate composition, method for producing isocyanate polymer and isocyanate polymer |
| EP3502089B1 (en) | 2017-12-20 | 2020-08-19 | 3M Innovative Properties Company | Process for the manufacturing of a 3-halopropionyl halide in a flow reactor |
| EP3502090B1 (en) | 2017-12-20 | 2020-08-19 | 3M Innovative Properties Company | Process for the manufacturing of a compound comprising a (meth)acryloyl group |
| WO2020040048A1 (en) * | 2018-08-20 | 2020-02-27 | 昭和電工株式会社 | Composition, production method for composition, and production method for unsaturated compound |
| TWI736952B (en) * | 2018-08-20 | 2021-08-21 | 日商昭和電工股份有限公司 | Composition, method for producing composition, and method for producing unsaturated compound |
| KR102611028B1 (en) | 2018-08-20 | 2023-12-08 | 가부시끼가이샤 레조낙 | Composition, method of making the composition and method of making the unsaturated compound |
| TWI777305B (en) * | 2018-08-20 | 2022-09-11 | 日商昭和電工股份有限公司 | Manufacturing method of the composition |
| WO2021141002A1 (en) * | 2020-01-06 | 2021-07-15 | 昭和電工株式会社 | (meth)acrylic acid ester compound having isocyanate group, and method for producing same |
| CN114315648B (en) * | 2022-01-11 | 2023-03-03 | 黎明化工研究设计院有限责任公司 | Method for reducing content of hydrolytic chlorine in isocyanate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2821544A (en) * | 1954-04-26 | 1958-01-28 | Bayer Ag | Production of alkylisocyanate esters of 2-alkenoic acids |
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| JPH0344378A (en) * | 1989-07-11 | 1991-02-26 | Nippon Zeon Co Ltd | Production of 5-fluorouracil derivative and polymer thereof |
| JP4273531B2 (en) * | 1998-02-06 | 2009-06-03 | 昭和電工株式会社 | Method for producing isocyanatoalkyl (meth) acrylate |
| US6245935B1 (en) * | 1998-02-06 | 2001-06-12 | Showa Denko Kabushiki Kaisha | Method for producing isocyanatoalkyl (meth)acrylate |
| DE19914292A1 (en) * | 1999-03-30 | 2000-10-05 | Bayer Ag | Reduction of the chorine content of low molecular isocyanates comprises reaction with a tertiary or quaternary amine group containing anion exchanger for ten minutes at less than two hundred degrees |
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2005
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2821544A (en) * | 1954-04-26 | 1958-01-28 | Bayer Ag | Production of alkylisocyanate esters of 2-alkenoic acids |
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| EP1745013B1 (en) | 2012-09-05 |
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| TW200604150A (en) | 2006-02-01 |
| TWI303627B (en) | 2008-12-01 |
| JP4823546B2 (en) | 2011-11-24 |
| WO2005092842A8 (en) | 2005-12-01 |
| EP1745013A1 (en) | 2007-01-24 |
| US20070197762A1 (en) | 2007-08-23 |
| US7632965B2 (en) | 2009-12-15 |
| KR100848433B1 (en) | 2008-07-28 |
| CN1934075A (en) | 2007-03-21 |
| JP2006232797A (en) | 2006-09-07 |
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